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WO1995012560A1 - Procede de traitement de dechets a l'aide d'acide concentre et produit ainsi obtenu - Google Patents

Procede de traitement de dechets a l'aide d'acide concentre et produit ainsi obtenu Download PDF

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Publication number
WO1995012560A1
WO1995012560A1 PCT/US1994/012230 US9412230W WO9512560A1 WO 1995012560 A1 WO1995012560 A1 WO 1995012560A1 US 9412230 W US9412230 W US 9412230W WO 9512560 A1 WO9512560 A1 WO 9512560A1
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WO
WIPO (PCT)
Prior art keywords
materials
acid
concentrated
resultant mixture
product
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1994/012230
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English (en)
Inventor
Harold W. Wilson
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Individual
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Individual
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Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to JP7513271A priority Critical patent/JPH09508566A/ja
Priority to EP95901044A priority patent/EP0726886A4/fr
Priority to AU10429/95A priority patent/AU700587B2/en
Publication of WO1995012560A1 publication Critical patent/WO1995012560A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
    • C05F11/00—Other organic fertilisers
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
    • C05F7/00—Fertilisers from waste water, sewage sludge, sea slime, ooze or similar masses
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses

Definitions

  • the present invention relates to processes for converting lignocellulose compounds, primarily waste newsprint, computer waste paper, waste paper in general, and waste wood such as saw dust and shredded wood into chemical compounds highly suitable for use among other applications in the beneficial treatment of all kinds and types of agricultural soils.
  • the present invention also relates to an unlimited number of new and extremely useful compositions-of-matter presently non-existent and unknown which can be produced by treating wood, particularly wood wastes (such as sawdust and the likes) , and/or treating paper, particularly waste paper (such as newsprint) , and/or treating other types of polysaccharides (matter composed essentially of cellulose and lignin) , preferably available as "wastes", with concentrated sulfuric acid (93 to 98.5% H 2 S0 4 ) , or with concentrated phosphoric acid (75 to 85% H 3 P0 4 ) , or with various combinations or mixtures of these acids in their concentrated forms.
  • the invention further contemplates that mixtures of wood waste and newspaper wastes treated with defined quantities of the concentrated phosphoric arid can be physically admixed with mixtures of wood and/or paper wastes that have already been treated with defined quantities of concentrated sulfuric acid to result in compositions-of-matter that demonstrate sources of soluble and available-to-plants (in soils) phosphorous pentoxide form of phosphorous in hydrate form; of soluble combined and uncombined phosphoric acid (H 3 P0 4 ) ; of soluble combined and uncombined sulfuric acid (H 2 S0 4 ) ; of hydrolyzed decomposed and partially undecomposed forms of organic matter; of available nitrogen; of lignin and certain ligno-organic compounds; of acetic acid; of both phosphoric and sulfur acid esters of cellulose and lignin; and additionally of sources of an extremely wide variety and number of both inorganic and organic chemical compounds all able to work in concert chemically and biologically when applied to agricultural soils in general
  • compositions-of-matter which have been produced by combining the above noted polysaccharide containing substances with the concentrated acids previously described.
  • the compositions-of-matter obtainable from use of the concerned processes can be made to contain variable amounts ranging between fractions of a percent to more than sixty (60%) percent of either concentrated sulfuric acid (H 2 S0 4 ) , concentrated phosphoric acid (H 3 P0 4 ) , or preselected mixtures of various amounts of both concentrated sulfuric acid and phosphoric acid in chemical and in physical combinations with the above noted lignocellulose compounds.
  • compositions-of-matter are also made to contain various contents of highly adsorbent carbonaceous matter including organic chemical compounds such as sulfuric and/or phosphoric acid esters of cellulose and lignin, pyrolytic products of reaction and heat decomposition, products of hydrolysis such as mixed aldehydes, ketones, degraded sugars and various organic acids such as acetic acid, all in combination with activated carbon and carbonaceous compounds having large capacities for adsorption of the many different highly water soluble acidic materials present in wide variations of kinds and amounts
  • a dry, solid product which is made to contain an equivalency of approximately 60% H 2 S0 4 can be made to react with variations of amounts of hydrated ammonia (NH 4 0H) to product compositions- of-matter having varying contents as desired of ammonium sulfate, (NH 4 ) 2 S0 4 in physical combination with amounts (as desired) of reactable but uncombined sulfuric acid per se.
  • NH 4 0H hydrated ammonia
  • This entire product can be sprayed with a sufficient amount of hydrated ammonia (NH 4 0H) solution to cause approximately one-half of the total sulfuric acid content to be neutralized to leave the other one-half of the acid content to remain unneutralized sulfuric acid - (H 2 S0 4 ) per se.
  • NH 4 0H hydrated ammonia
  • Equation 2 ( 42 gms . AmSO 4 - H 2 0 - 24 . 5 gms . H 2 S0 4 )
  • the resultant products can be totally neutralized to form ammonium and ammonium acid phosphate salt derivatives; or the acid can be only partially neutralized to form products containing variable amounts of a mixture of neutralized ammonium phosphate compounds and non-neutralized phosphoric acid per se in the presence of the lignocellulosic matter.
  • Nitrogen-containing basic compounds such as urea can be admixed with the acidic products of concentrated acid processed lignocellulose to result in the formation of urea sulfate and/or urea phosphate amide salts of variable compositions depending upon the selected acid, the amount used, and the amount of urea or other nitrogen-containing compounds used in such treatments.
  • Such products in addition to having the contents of phosphate in plant-available form will also have contents of activated carbon, carbonaceous matter and organic matter holding the available phosphate as acid phosphate by adsorption and absorption in a cellulosic-acid matrix which has a longer "life" in the soil profile than is displayed by "conventional super-phosphate” products.
  • the water soluble and reactable acid contents of the products which can be made by the processes of this invention are capable of acidification of additional amounts of similar or dissimilar cellulose and lignocellulose materials in addition to being capable of reacting with other reactable substances (such as free alkali in soils) .
  • reactable substances such as free alkali in soils
  • approximately 850 grams of representative product was made by use of the concerned processes where 350 grams of sawdust having a water content of approxi ately 35% were combined with 650 grams of concentrated sulfuric acid (98.5% H 2 S0 4 ) with the concentrated sulfuric acid being poured in one constant stream directly upon the sawdust while the two substances were thoroughly combined.
  • the resultant mixture was air dried at temperatures between 225° and 300°F to result in approximately 850 grams of free flowing, dry product having a soluble acid equivalence of approximately 70% expressed as percentage H 2 S0 4 .
  • the product contained a percentage of water soluble compounds of approximately 82% of which, in addition to the sulfuric acid, consisted of water soluble organic compounds and a small content of acid bound water.
  • the water insoluble matter amounting to approximately 17% consisted of a mixture of approximately 45% activated carbon and 55% activated organic carbonaceous matter with an ash content determined to amount to approximately 0.5% of the water insoluble matter.
  • Such activated carbon compounds coupled with a presence of a number of sulfated organic compounds like fatty alcohols, fatty acid amides, fatty acid esters, secondary alcohol sulfates, sulfated esters, and sulfated dibasic acids, among other sulfuric acid and phosphoric acid reactant products (being anionic surfactants and excellent wetting agents) give the cellulose and the cellulose esters in these products tremendous adsorption and surfactant capacities, even to the extent of their ability to adsorb suspensions along with enhancing easier and more complete decomposition of any halogenated organic matter which may be present in soils while working in conjunction with lignin fractions in the attraction and destruction of white rot fungi and several other undesirable fungal growths that may be present in soils.
  • the present invention relates to original and previously undisclosed compositions-of-matter along with the processes most suitable for use for their preparations.
  • the invention includes multiple compositions, uses, and accompanying values, all illustrating new and very useful conversions of common waste material into useful compositions-of-matter.
  • the following examples are considered to be illustrative of my invention for converting wood wastes, waste paper, and any substance consisting essentially of cellulose-lignin-polysaccharides into dry, solid compositions-of-matter especially most suitable for use in the field of agricultural chemistry, but also applicable for use in other fields of chemistry.
  • EXAMPLE 1 EXAMPLE 1:
  • garbage wastes commonly referred to as municipal solid wastes known as garbage
  • garbage sewage sludges as produced in municipal sewage treatment plants.
  • garbage consists essentially of the following materials; 46.9% paper and cardboard, 8.5% wood, 8.4% food wastes, 3.5% textiles, 10.4% plastics, 20.3% yard waste, and a balance of approximately 2% of unidentified extraneous matter.
  • garbage is composed of essentially cellulose and lignocellulosic materials for the most part.
  • Municipal sewage sludges also contain large amounts of reactable cellulose lignocellulose in addition to having contents of human and animal wastes, soil, and extraneous matter. All of the samples of garbage and sewage sludges obtained from a number of sources demonstrated excellent amenabilities to being treated by the processes of the instant invention for their conversion either into materials most suitable for inclusion into landfills or into chemical products suitable for application to all types of agricultural soils to provide requisite plant nutrients in addition to being particularly useful for beneficiation of agricultural soils.
  • the action of the concentrated acid used and the steam-heat generated when the concentrated acid is initially brought into contact as concentrate acid with the garbage or the sewage sludge (or even mixtures of these materials) is highly effective in destroying saprophytic matter such as fungi and molds as well as any bacteria and ther ophilic organisms that may be present.
  • the additional processing comprises "drying" the products at temperatures ranging between 225° and 300°F. During the drying step, moisture (as steam) is released from the products while the acid concentration is increased further.
  • the presence of the sulfate and/or phosphate radicals materially aid in oxidizing and detoxifying odorous sulfide sulfur compounds, amines, and benzopyrroles (from protein putrefaction) such as the chemical compounds indole and skatole (which cause the daunting odors from the benzopyrroles contained in most human waste matter) .
  • the mechanisms of the actions of the oxygen radicals are shown below: so;
  • the presence of the methoxyl group - (CH 3 0") - on the acetic acid increases ionization by facilitating separation of the hydroxylic hydrogen as a proton promoting electron attraction to further enhance detoxification of odorous entities contained in sewage sludges.
  • the principal effect of the organic matter present in products derived from use of this invention is not solely for making agricultural soils acidic in nature, but primarily for use in increasing the soil buffering capacity of such soils. In arid land soils especially, very small amounts of organic matter are found present until such soils are brought into agricultural production through irrigation.
  • the products considered to be most basic to this invention have variable contents to both combined and uncombined sulfuric and/or phosphoric acids
  • the products in the event the products are designed for use for beneficiation of highly acidic type soils, the products (as formed by treatment of cellulose and/or lignocellulose with concentrated sulfuric and/or phosphoric acids) can be additionally treated with alkaline materials such as, for example, lime or limestone to neutralize some, any part of, or all of any content of free acids present in the organic matter product under consideration.
  • CaO calcium oxide
  • the advantage of using products such as the cellulosic materials used in the instant invention is that a large amount and number of acidic organic groups held together in large molecular aggregates as represented by cellulose and lignin acid sulfate and acid phosphate esters (after being treated with the concentrated acids described) present in soils as organic matter structures are highly resistant to attack and immediate destruction by micro-organisms.
  • the presence of such organic groups act to improve overall soil structures, while interacting with surfaces of clay minerals present in the soil and providing soil nutrients and soil beneficiation all at the same time.
  • This invention was developed primarily to provide processes to permit the useful disposition of waste matter by converting such matter into useful agricultural chemicals. However, it was anticipated that if the amounts of available waste exceed the amount that could and would be used in converted forms as agricultural chemicals, then one of the prime values of the invention from acidification of the waste cellulosic matter with concentrated acids would be derived since the acidification process of itself results in a 30% to 65% reduction of the overall volumes, in most cases, of such wastes processed. This volume reduction alone would, at least on average, double the volume of landfill availability.
  • the product can be made to contain defined amounts of available acid in terms of either, or both, concentrated sulfuric or phosphoric acids, and this available acid will react with previously untreated cellulose, lignocellulose, carbohydrates, and proteinaceous matter already present in landfills to degrade such materials, their volumes in turn will be reduced and the presence of the oxidative S0 4 * (sulfate) and P0 4 * (phosphate) radicals will allay the possibility of toxicity and assist in the conversion of malodorous matter by oxidation into non-odorous matter.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Processing Of Solid Wastes (AREA)
  • Soil Conditioners And Soil-Stabilizing Materials (AREA)
  • Fertilizers (AREA)

Abstract

Procédé de traitement de bois, en particulier de déchets de bois (tels que sciure et analogue) et/ou de papier, en particulier de papiers usés (tels que des journaux) et/ou d'autres types de polysaccharides (matière composée essentiellement de cellulose et de lignine), de préférence disponibles sous forme de 'déchets', avec de l'acide sulfurique concentré (93 à 98,5 % de H2SO4) ou avec de l'acide phosphorique concentré (75 à 85 % de H3PO4), ou avec différents mélanges de ces acides dans leur forme concentrée. Le produit résultant dudit procédé peut être utilisé pour traiter des sols agricoles ou peut être mis en décharge.
PCT/US1994/012230 1993-11-03 1994-10-27 Procede de traitement de dechets a l'aide d'acide concentre et produit ainsi obtenu Ceased WO1995012560A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP7513271A JPH09508566A (ja) 1993-11-03 1994-10-27 廃棄物材料の濃酸による処理法及びこの方法により製造された生成物
EP95901044A EP0726886A4 (fr) 1993-11-03 1994-10-27 Procede de traitement de dechets a l'aide d'acide concentre et produit ainsi obtenu
AU10429/95A AU700587B2 (en) 1993-11-03 1994-10-27 Process for treating waste materials with concentrated acid and the product produced thereby

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/145,218 US5486068A (en) 1993-11-03 1993-11-03 Process for treating waste materials with concentrated acid and the product produced thereby
US08/145,218 1993-11-03

Publications (1)

Publication Number Publication Date
WO1995012560A1 true WO1995012560A1 (fr) 1995-05-11

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PCT/US1994/012230 Ceased WO1995012560A1 (fr) 1993-11-03 1994-10-27 Procede de traitement de dechets a l'aide d'acide concentre et produit ainsi obtenu

Country Status (6)

Country Link
US (1) US5486068A (fr)
EP (1) EP0726886A4 (fr)
JP (1) JPH09508566A (fr)
AU (1) AU700587B2 (fr)
CA (1) CA2175561A1 (fr)
WO (1) WO1995012560A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001068562A3 (fr) * 2000-03-13 2002-04-11 Energy Engineering Internat Pt Production d'un produit fertilisant
WO2010014503A1 (fr) * 2008-07-31 2010-02-04 E.I. Du Pont De Nemours And Company Décristallisation de biomasse cellulosique avec un mélange d'acides comprenant des acides phosphorique et sulfurique
RU2562526C2 (ru) * 2013-09-26 2015-09-10 Федеральное государственное бюджетное учреждение науки Центр по проблемам экологии и продуктивности лесов Российской академии наук Способ биотехнологической переработки твердых отходов целлюлозно-бумажной промышленности для получения биогумуса, включающий стадию обработки грибами и стадию вермипереработки
WO2015179987A1 (fr) 2014-05-30 2015-12-03 Sulvaris Inc. Engrais à libération lente, à base de biomasse éclatée

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5674806A (en) * 1994-04-15 1997-10-07 Adamoli, Jr.; James R. Using aggregates containing cellulose for agricultural and horticultural purposes
US5951995A (en) * 1994-04-15 1999-09-14 Adamoli, Jr.; James R. Uses for cellulose-containing aggregates
US5876505A (en) * 1998-01-13 1999-03-02 Thermo Fibergen, Inc. Method of producing glucose from papermaking sludge using concentrated or dilute acid hydrolysis
US6312492B1 (en) 1999-09-21 2001-11-06 Harold W. Wilson Beneficiation of animal manure
EP1409130B1 (fr) * 2001-07-17 2004-11-10 Zhi-Wei Liang Processus de sechage thermochimique oxydatif destine a modifier les caracteristiques hydrophiles/hydrophobes de substances organiques naturelles
US6800109B1 (en) * 2002-05-03 2004-10-05 Adelbert Carlen Organic waste treatment system
US8317975B2 (en) 2004-04-20 2012-11-27 The Research Foundation Of The State University Of New York Product and processes from an integrated forest biorefinery
US9708208B2 (en) * 2006-07-18 2017-07-18 Hyperthermics Holding As Energy production with hyperthermophilic organisms
US8278087B2 (en) * 2006-07-18 2012-10-02 The University of Regensburg Energy production with hyperthermophilic organisms
EP2081676B1 (fr) 2006-08-23 2016-05-25 Carbon Solutions Inc. Procédé de préparation du charbon actif imprégné d'acide et son utilisation
EP2352878A1 (fr) * 2008-11-20 2011-08-10 E. I. du Pont de Nemours and Company Production de sucre par décristallisation et hydrolyse de biomasse enrichie en polysaccharide
WO2011082974A1 (fr) * 2009-12-16 2011-07-14 Basf Se Adsorption des boues acides d'eaux usées dinitrotoluène
CN101891361A (zh) * 2010-07-02 2010-11-24 贵州新欣环保投资有限责任公司 一种城市生活污泥处理方法
EP3655588B1 (fr) * 2017-07-17 2021-07-14 Nastev, Viktor Dispositif à actionnement électrique ou pneumatique d'un mécanisme repliable pour encourager la réduction d'une vitesse de véhicule
KR101962239B1 (ko) * 2017-12-06 2019-03-27 주식회사 리그넘 플라스틱 첨가용 바이오 충진제를 제조하는 방법 및 이에 의해 제조된 플라스틱 첨가용 바이오 충진제
WO2021205960A1 (fr) * 2020-04-09 2021-10-14 昭和電工株式会社 Procédé pour la fabrication d'un engrais
US12384988B2 (en) 2021-06-09 2025-08-12 Kroff Landfill Technologies, Inc. Method and composition for removing a landfill residue

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US2985643A (en) * 1956-01-03 1961-05-23 Wooduse Inc Process for conversion of lignocellulose materials
US3218149A (en) * 1963-02-25 1965-11-16 Chesapeake Corp Of Virginia Method of making fertilizer, mulch and soil conditioner
US3758287A (en) * 1972-08-28 1973-09-11 Western Minerals Inc Process of treating organic waste
US4343646A (en) * 1979-12-10 1982-08-10 Calspan Corporation Method for producing fertilizer from waste paper
US5161915A (en) * 1991-03-25 1992-11-10 Landfill Service Corporation Synthetic cover for waste piles

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US2362390A (en) * 1940-08-03 1944-11-07 Quaker Oats Co Manufacture of furfural and fertilizer
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US2985643A (en) * 1956-01-03 1961-05-23 Wooduse Inc Process for conversion of lignocellulose materials
US3218149A (en) * 1963-02-25 1965-11-16 Chesapeake Corp Of Virginia Method of making fertilizer, mulch and soil conditioner
US3758287A (en) * 1972-08-28 1973-09-11 Western Minerals Inc Process of treating organic waste
US4343646A (en) * 1979-12-10 1982-08-10 Calspan Corporation Method for producing fertilizer from waste paper
US5161915A (en) * 1991-03-25 1992-11-10 Landfill Service Corporation Synthetic cover for waste piles

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Title
See also references of EP0726886A4 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001068562A3 (fr) * 2000-03-13 2002-04-11 Energy Engineering Internat Pt Production d'un produit fertilisant
WO2010014503A1 (fr) * 2008-07-31 2010-02-04 E.I. Du Pont De Nemours And Company Décristallisation de biomasse cellulosique avec un mélange d'acides comprenant des acides phosphorique et sulfurique
CN102112633A (zh) * 2008-07-31 2011-06-29 纳幕尔杜邦公司 包含磷酸和硫酸的酸混合物对纤维质生物质的消晶作用
RU2562526C2 (ru) * 2013-09-26 2015-09-10 Федеральное государственное бюджетное учреждение науки Центр по проблемам экологии и продуктивности лесов Российской академии наук Способ биотехнологической переработки твердых отходов целлюлозно-бумажной промышленности для получения биогумуса, включающий стадию обработки грибами и стадию вермипереработки
WO2015179987A1 (fr) 2014-05-30 2015-12-03 Sulvaris Inc. Engrais à libération lente, à base de biomasse éclatée
EP3148956A4 (fr) * 2014-05-30 2018-01-17 Sulvaris Inc. Engrais à libération lente, à base de biomasse éclatée
AU2015268027B2 (en) * 2014-05-30 2019-11-14 Sulvaris Inc. Exploded biomass based slow-release fertilizer
US10981842B2 (en) 2014-05-30 2021-04-20 Sulvaris Inc. Exploded biomass based slow-release fertilizer

Also Published As

Publication number Publication date
JPH09508566A (ja) 1997-09-02
AU700587B2 (en) 1999-01-07
EP0726886A1 (fr) 1996-08-21
EP0726886A4 (fr) 1998-07-01
CA2175561A1 (fr) 1995-05-11
US5486068A (en) 1996-01-23
AU1042995A (en) 1995-05-23

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